Catalyst composition for the polymerization of olefins

ABSTRACT

A catalyst composition for the polymerization of olefins is provided, which comprises the reaction product of a fulvene, a complex of an atom selected from Groups 3-14 and the Lanthanides, and an activating cocatalyst.

CROSS REFERENCE STATEMENT

This application is a divisional of U.S. Ser. No. 08/999,148, filed Dec.29, 1997, now U.S. Pat No. 6,054,405.

The present invention provides a catalyst composition for thepolymerization of olefins, which comprises the reaction product of afulvene, a complex of an atom selected from Groups 3-14 and theLanthanides, and an activating cocatalyst.

BACKGROUND OF THE INVENTION

In the field of single-site polymerization of olefins, typical catalystcompositions comprise organometallic catalysts such as metallocenescontacted with activating cocatalysts such as alumoxanes. The synthesisand isolation of metallocenes can be difficult due to their air andmoisture sensitivity. Yields are often poor with more complex kinds ofcatalysts. Thus, catalyst cost can be substantial. Moreover, it isdifficult to change substantially the rates and product properties ofthese catalysts once they have been made, since the ligand of thecatalyst exerts overwhelming control over the catalyst compositionproperties. Thus, such catalysts are not especially amenable toprocesses using a variety of conditions or producing a variety ofproducts.

Catalyst compositions that can be assembled at the site of the reactorare advantageous in terms of cost because isolation and purification isavoided. Moreover, catalysts previously considered non-isolable orcatalysts that could not even be made in impure form can be readily madeby self-assembly. Self-assembled catalyst compositions can also beextremely versatile. Catalyst composition properties can be tuned byadjusting the various components of the catalyst composition.

U.S. Pat. Nos. 5,378,567 and 5,451,555 to Tajima et al. relate tocatalyst compositions for the homopolymerization or copolymerization ofolefins. The catalyst compositions comprise a first compound of theformula Me¹(OR¹)_(p)R² _(q)X¹ _(4−p−q), wherein Me¹ is Ti, Zr, or Hf, asecond compound of the formula Me²(OR³)_(m)R⁴ _(n)X² _(z−m−n), whereinMe² is a Group I-III metal, and a third compound that is an organocycliccompound having two or more conjugated double bonds. A variety oforganocyclic compounds are described in these patents, none of which arefulvenes.

Similarly, U.S. Pat. No. 5,331,071 to Kataoka et al. describes a processfor the polymerization of olefinic hydrocarbons carried out in thepresence of a catalyst component derived from reacting a compound of theformula Me¹R¹ _(n)X¹ _(4−n), wherein Me¹ is Ti, Zr, or Hf, a compound ofthe formula Me²R² _(m)X² _(z−m), wherein Me² is a Group I-III metal, anorganocyclic compound having two or more conjugated double bonds, and aninert carrier, along with a modified organoaluminum compound havingAl—O—Al bonds. Again, a variety of organocyclic compounds are described,none of which are fulvenes.

U.S. Pat. No. 5,158,920 to Razavi discloses a process for thepreparation of a bridged metallocene catalyst. The bridgedcyclopentadienyl ligand of the catalyst is made by reacting acyclopentadiene with substituted fulvene. The ligand is isolated andthen contacted with a transition metal halide or hydrocarbon compound toform the bridged metallocene catalyst. Cocatalyst is subsequently added.

Derwent Abstract 96-088466/10 for DE 4434640 relates to the in situproduction of a bridged metallocene catalyst by reacting acyclopentadiene with a base, a bridging reagent, and a metal compound.The resulting stereorigid catalyst may be used for the polymerization ofolefins.

Applicant has now discovered a self-assembled catalyst composition thatmay be easily and cost effectively made. The catalyst compositioncomprises the reaction product of a fulvene, a complex of an atomselected from Groups 3-14 and the Lanthanides, and an activatingcocatalyst. The catalyst composition may contain a solvent as well, andis preferably used in unsupported, liquid form. Isolation of thecatalyst composition or intermediates thereto is not required.Combinations of different fulvenes, complexes of an atom selected fromGroups 3-14 and the Lanthanides, and activating cocatalysts can lead toversatile catalyst compositions that can be altered on-stream to matchproduct and process requirements. Conditions used during catalystcomposition formation such as temperature and concentrations of thereactants also can be used to control the properties of the resultingcatalyst composition and polymer product.

SUMMARY OF THE INVENTION

The invention provides a catalyst composition comprising the reactionproduct of:

a) a fulvene of the formula:

including oligomers thereof,

wherein each R₁, R₂, R₃, R₄, R₅, and R₆ is independently hydrogen,hydrocarbyl, or a heteroatom-containing group; and any two or more Rgroups may be joined to form a ring;

b) a complex of the formula [L_(m)MX_(n)]_(r) wherein each L is aneutral ligand, M is an atom selected from Groups 3 to 14 and theLanthanides, each X is an anionic group, m is an integer of 0 orgreater, n is an integer of 0 or greater; and r is an integer of 1 orgreater; and

c) an activating cocatalyst.

The invention also provides a process for the polymerization of olefins,which comprises contacting under polymerization conditions olefin with acatalyst composition comprising the reaction product of.

a) a fulvene of the formula:

including oligomers thereof,

wherein each R₁, R₂, R₃, R₄, R₅, and R₆ is independently hydrogen,hydrocarbyl, or a heteroatom-containing group; and any two or more Rgroups may be joined to form a ring;

b) a complex of the formula [L_(m)MX_(n)]_(r) wherein each L is aneutral ligand, M is an atom selected from Groups 3 to 14 and theLanthanides, each X is an anionic group, m is an integer of 0 orgreater, n is an integer of 0 or greater; and r is an integer of 1 orgreater; and

c) an activating cocatalyst.

DETAILED DESCRIPTION OF THE INVENTION

The catalyst composition comprises the reaction product of at least onefulvene, at least one complex of an atom selected from Groups 3-14 andthe Lanthanides, and at least one activating cocatalyst.

The fulvene has the formula:

wherein each R₁, R₂, R₃, R₄, R₅, and R₆ is independently hydrogen;hydrocarbyl such as alkyl, aryl, alkenyl, or alkynyl; or aheteroatom-containing group such as alkoxy, aryloxy, amino, halo, asilicon atom, or silicon-containing group. A heteroatom-containing groupis any group containing at least one atom that is not carbon orhydrogen. Preferably, any hydrocarbyl group contains from 1 to 50 carbonatoms. Similarly, any alkoxy or aryloxy group preferably contains from 1to 50 carbon atoms. Any two or more R groups may be joined to form aring. In the case of R₃ through R₆, two adjacent R groups may compriseone or more arene rings fused to the cyclopentadiene ring.

Furthermore, two or more such fulvene moieties can be linked by one ormore linking groups such as hydrocarbyls or heteroatom-containing groupsto form a dimer or other oligomer. As used herein, an oligomer of afulvene means two or more fulvenes linked together by such linkinggroups.

Examples of fulvenes include fulvene, 6-methylfulvene,6,6-dimethylfulvene, 6-phenylfulvene, 6-methyl-6-phenylfulvene,6-t-butylfulvene, 6-benzylfulvene, 6,6-trimethylenefulvene,6,6-tetramethylenefulvene, 6,6-pentamethylenefulvene,6,6-hexamethylenefulvene, 2-norbornylidenecyclopentadiene,2-adamantylidenecyclopentadiene, 3,6,6-trimethylfulvene,3-t-butyl-6,6-dimethylfulvene, 3-methyl-6,6-pentamethylenefulvene,1-isopropylideneindene, 1-ethylideneindene, 1-benzylideneindene,9-isopropylidenefluorene, 6-vinylfulvene, 6,6-divinylfulvene,cyclopropenylidenecyclopentadiene, cyclopentadienylidenecyclopentadiene,cycloheptatrienylidenecyclopentadiene, and azulene.

Preferred fulvenes include 6-t-butylfulvene and 6,6-dialkylfulvenes suchas 6,6-dimethylfulvene, 6-methyl-6-phenylfulvene,6,6-tetramethylenefulvene, and 6,6-pentamethylenefulvene. Most preferredis 6,6-pentamethylenefulvene.

The fulvene may be made in any manner. One useful synthesis method fromcommon precursors is described in Neuenschwander, M., The Chemistry ofDouble-Bonded Functional Groups; Patai, S. Ed.; John Wiley and Sons,Ltd. 1989. Another method of making the fulvene is given in Stone, K.J.; Little, R. D. J. Org. Chem. 1984, 49, 1849.

The complex of an atom selected from Groups 3-14 and the Lanthanides hasthe formula [L_(m)MX_(n)]_(r). Each L is the same or different neutralligand, such as Et₂O, tetrahydrofuran, Et₃N, or pyridine.

M is an atom selected from Groups 3 to 14 of the Periodic Table and theLanthanides. Preferably, M is an element selected from Groups 3 to 6 andthe Lanthanides. More preferably, M is a Group 4 element.

Each X is the same or different anionic group, such as halide, alkoxide,amide, hydrocarbyl, acetylacetonate, carboxylate, carbamate, amidate, oraluminate anion such as tetramethylaluminate or tetrachloroaluminate.

The letter m is an integer of 0 or greater, the letter n is an integerof 0 or greater; and the letter r is an integer of 1 or greater

Examples of the complex of an atom selected from Groups 3-14 and theLanthanides include titanium (IV) chloride, titanium (IV) bromide,titanium (IV) iodide, titanium (IV) diethylamide, titanium (IV)t-butoxide, titanium (IV) acetylacetonate, zirconium (IV) chloride,zirconium (IV) bromide, zirconium (IV) iodide, zirconium (IV)diethylamide, zirconium (IV) t-butoxide, zirconium tetrabenzyl,zirconium (IV) acetylacetonate, zirconium an perfluoroacetylacetonate,zirconium (IV) pivalate, zirconium (IV) diethylcarbamate, zirconiumdichloride bis(acetylacetonate), hafnium (IV) chloride, hafnium (IV)bromide, hafnium (IV) iodide, hafnium (IV) diethylamide, hafnium (IV)t-butoxide, hafnium tetrabenzyl, hafnium (IV) acetylacetonate, hafnium(IV) pivalate, hafnium (IV) diethylcarbamate, and hafnium dichloridebis(acetylacetonate).

Preferred complexes of an atom selected from Groups 3-14 and theLanthanides include zirconium (IV) chloride, zirconium (IV) bromide,zirconium (IV) diethylamide, and zirconium (IV) acetylacetonate. Mostpreferred are zirconium (IV) acetylacetonate and zirconium (IV)diethylamide.

The activating cocatalyst preferably is selected from alumoxanes such asmethylalumoxane, modified methylalumoxane (MMAO), and isobutylalumoxane.Boron alkyls, boron aryls, and organoaluminum compounds such astriisobutylaluminum and diethylaluminum chloride, can also be used. Theactivating cocatalyst can be neat, in solution, or supported on asuitable support. Most preferred as the activating cocatalyst is MMAO inan aliphatic hydrocarbon solvent. With some catalyst compositionsaccording to the invention, it is preferred to use a mixture ofactivating cocatalysts.

Optionally, the catalyst composition may also comprise an olefinadjuvant. It has been found that olefin adjuvants added to the catalystcomposition during its formation increase the activity of catalystcomposition. Suitable olefin adjuvants include ethylene, propylene,1-butene, 2-butene, 1-hexene, isobutylene, diisobutylene, and dienes.Preferred are 1-butene and 1-hexene.

The catalyst composition is preferably used in unsupported, liquid form,such as a solution, dispersion, or neat liquid as described in U.S. Pat.No. 5,317,036, or formed in-situ during polymerization. It is mostpreferred to use the catalyst composition as a solution in one or moresolvents to facilitate handling. Preferred solvents include pentane,hexane, isopentane and toluene. The catalyst components need not besoluble in the solvent(s).

The catalyst composition may also be impregnated onto a solid, inertsupport, spray dried as described in U.S. Pat. No. 5,648,310, or in theform of a prepolymer. In the case of a supported catalyst composition,the catalyst composition, once formed, may be impregnated in ordeposited on the surface of an inert substrate such as silica, carbonblack, polyethylene, polycarbonate porous crosslinked polystyrene,porous crosslinked polypropylene, alumina, thoria, zirconia, ormagnesium halide (e.g., magnesium dichloride), such that the catalystcomposition is between 0.1 and 90 percent by weight of the total weightof the catalyst composition and the support.

Catalyst composition assembly, i.e., contacting of the fulvene, thecomplex of an atom selected from Groups 3-14 and the Lanthanides, theactivating cocatalyst, and optionally the olefin adjuvant, can becarried out under a variety of conditions. The order of addition andconcentration of the catalyst components, and the time, temperature,solvent if used, and pressure during contacting may vary.

The catalyst components can be mixed in any order. The preferred orderof addition depends on the nature of the fulvene, the complex of an atomselected from Groups 3-14 and the Lanthanides, the solvent (if used),and the activating cocatalyst, as well as the desired product.

The time of contacting the catalyst components can be varied from about0.1 seconds to about 24 hours. The preferred time depends on theconditions but is normally around 30 minutes.

The temperature of contacting can be varied from around −80° C. to 100°C. but the preferred temperature is around 25° C.

Pressure for contacting ranges from 0 to 500 psi, preferably aroundatmospheric pressure.

The concentration of each catalyst component varies from 1 mM to about10 M during contacting. For example, when contacting a fulvene, azirconium compound, an aluminoxane, and an olefin adjuvant to make thecatalyst composition, the concentration of fulvene is most preferablyabout 0.002 M, the concentration of zirconium is most preferably about0.001M, the concentration of Al is most preferably about 0.1 M, and theconcentration of the olefin adjuvant is most preferably about 10 volumepercent during contacting.

The catalyst composition may be used for the polymerization of olefinsby any suspension, solution, slurry, or gas phase process, using knownequipment and reaction conditions, and is not limited to any specifictype of reaction system. Generally, olefin polymerization temperaturesrange from about 0° C. to about 200° C. at atmospheric, subatmospheric,or superatmospheric pressures. Slurry or solution polymerizationprocesses may utilize subatmospheric or superatmospheric pressures andtemperatures in the range of about 40° C. to about 110° C. A usefulliquid phase polymerization reaction system is described in U.S. Pat.No. 3,324,095. Liquid phase reaction systems generally comprise areactor vessel to which olefin monomer and catalyst composition areadded, and which contains a liquid reaction medium for dissolving orsuspending the polyolefin. The liquid reaction medium may consist of thebulk liquid monomer or an inert liquid hydrocarbon that is nonreactiveunder the polymerization conditions employed. Although such an inertliquid hydrocarbon need not function as a solvent for the catalystcomposition or the polymer obtained by the process, it usually serves assolvent for the monomers employed in the polymerization. Among the inertliquid hydrocarbons suitable for this purpose are isopentane, hexane,cyclohexane, heptane, benzene, toluene, and the like. Reactive contactbetween the olefin monomer and the catalyst composition should bemaintained by constant stirring or agitation. The reaction mediumcontaining the olefin polymer product and unreacted olefin monomer iswithdrawn from the reactor continuously. The olefin polymer product isseparated, and the unreacted olefin monomer and liquid reaction mediumare recycled into the reactor.

Preferably, gas phase polymerization is employed, with superatmosphericpressures in the range of 1 to 1000 psi, preferably 50 to 400 psi, mostpreferably 100 to 300 psi, and temperatures in the range of 30 to 130°C., preferably 65 to 110° C. Stirred or fluidized bed gas phase reactionsystems are particularly useful. Generally, a conventional gas phase,fluidized bed process is conducted by passing a stream containing one ormore olefin monomers continuously through a fluidized bed reactor underreaction conditions and in the presence of catalyst composition at avelocity sufficient to maintain a bed of solid particles in a suspendedcondition. A stream containing unreacted monomer is withdrawn from thereactor continuously, compressed, cooled, optionally fully or partiallycondensed as disclosed in U.S. Pat. Nos. 4,528,790 and 5,462,999, andrecycled to the reactor. Product is withdrawn from the reactor andmake-up monomer is added to the recycle stream. As desired fortemperature control of the system, any gas inert to the catalystcomposition and reactants may also be present in the gas stream. Inaddition, a fluidization aid such as carbon black, silica, clay, or talcmay be used, as disclosed in U.S. Pat. No. 4,994,534.

Polymerization may be carried out in a single reactor or in two or morereactors in series, and is conducted substantially in the absence ofcatalyst poisons. Organometallic compounds may be employed as scavengingagents for poisons to increase the catalyst activity. Examples ofscavenging agents are metal alkyls, preferably aluminum alkyls, mostpreferably triisobutylaluminum, and aluminoxanes.

Conventional adjuvants may be included in the process, provided they donot interfere with the operation of the catalyst composition in formingthe desired polyolefin. Hydrogen or a metal or non-metal hydride, e.g.,a silyl hydride, may be used as a chain transfer agent in the process.Hydrogen may be used in amounts up to about 10 moles of hydrogen permole of total monomer feed.

Olefin polymers that may be produced according to the invention include,but are not limited to, ethylene homopolymers, homopolymers of linear orbranched higher alpha-olefins containing 3 to about 20 carbon atoms, andinterpolymers of ethylene and such higher alpha-olefins, with densitiesranging from about 0.86 to about 0.96. Suitable higher alpha-olefinsinclude, for example, propylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-octene, and 3,5,5-trimethyl-l-hexene. Olefinpolymers according to the invention may also be based on or containconjugated or non-conjugated dienes, such as linear, branched, or cyclichydrocarbon dienes having from about 4 to about 20, preferably 4 to 12,carbon atoms. Preferred dienes include 1,4-pentadiene, 1,5-hexadiene,5-vinyl-2-norbornene, 1,7-octadiene, vinyl cyclohexene,dicyclopentadiene, butadiene, isobutylene, isoprene, ethylidenenorbornene and the like. Aromatic compounds having vinyl unsaturationsuch as styrene and substituted styrenes, and polar vinyl monomers suchas acrylonitrile, maleic acid esters, vinyl acetate, acrylate esters,methacrylate esters, vinyl trialkyl silanes and the like may bepolymerized according to the invention as well. Specific olefin polymersthat may be made according to the invention include, for example,polyethylene, polypropylene, ethylene/propylene rubbers (EPR's),ethylene/propylene/diene terpolymers (EPDM's), polybutadiene,polyisoprene and the like.

The following non-limiting examples further illustrate the invention.

EXAMPLES

Synthesis of the fulvenes was accomplished using the general procedureoutlined in Stone, K. J.; Little, R. D. J. Org. Chem. 1984, 49, 1849.

Activity was measured in g polyethylene/mmol metal-hr 100 psi ethylene.

General Procedure for Slurry Polymerization Reactions

Polymerization experiments were conducted in a one liter, computeroperated, slurry reactor with an air-operated, magnetically coupledstirrer and an outer steam-heated shell and an inner acetoneheat-transfer shell.

The reactor was dried by heating to 100° C. while purging with 500 sccmof nitrogen for 30 minutes. Hexene and catalyst composition solutionwere then injected using disposable polypropylene syringes with 12″ (18gauge) s.s. oven-dried needles. The reactor was heated to a pre-heattemperature (usually 55° C.) and half of the modified methylalumoxane(MMAO Type 3A commercially available from Akzo Chemicals, Inc., 6.7-7.1wt % Al in heptane) charge was added to the reactor as acocatalyst/scavenger.

Meanwhile, the fulvene and the complex of an atom selected from Groups3-14 and the Lanthanides were mixed with the remainder of the alumoxanein a drybox and charged to a syringe. This mixture was then injectedinto the reactor and the reactor sealed. If an olefin adjuvant was used,this was mixed with the fulvene/complex of an atom selected from Groups3-14 and the Lanthanides mixture prior to contacting with the alumoxane.

Ethylene was pre-fed at 3000 sccm for one minute with stirring, thenheated to reaction temperature. Ethylene was initially fed into thereactor at 40 psi higher than the reaction pressure, at which time thestirring began causing ethylene to be absorbed into the hexane. Thecomputer maintained selected pressure and temperature for the durationof the run. At the end of the reaction, the computer cooled,depressurized and purged the system with nitrogen.

The recovered polymer was vacuum filtered through #4 paper and dried ina vacuum oven at 55° C. The dry resin was treated with 1000 ppm of B900blended antioxidant stabilizer (1 pt. Irganox 1076 & 4 pts. Irgafos 168)and pulverized in a Waring blender before any analysis.

Examples 1-24

In Examples 1-22 a series of ethylene/1-hexene copolymers were madeusing the slurry polymerization technique outlined above with catalystcompositions according to the invention made from a variety of fulveneswith Zr(NEt₂)₄ and MMAO. Examples 23 and 24 are comparative.

In each of Examples 1-24, the catalyst composition was formed by firstdissolving 50 μmol of the ligand shown in Table 1 and 9.5 mg Zr(NEt₂)₄(25 μmol) in 18 mL of dry toluene in the glove box. To this solution wasadded 7.0 mL MMAO to make a [Zr]=1 mM stock solution. After aging 30minutes, an appropriate aliquot of this stock solution was then injectedinto the reactor, which contained 600 mL of hexane, 43 mL of 1-hexeneand sufficient MMAO (to make the final Al/Zr ratio 1000) at 55° C. Thepolymerization reaction was conducted at 75° C. under 85 psi ethylenefor 30 minutes.

The results are shown in Table 1 below.

TABLE 1 g PE/ mmol Zr/ Exam- μmo 100 psi/ ple ligand IZr hr 1

0.5 212706 2

1   111529 3

0.5 100235 4

1.5  91137 5

1    83294 6

1    74118 7

1    57882 8

0.5  34824 9

3    33569 10 

1    10824 11 

3    5804

12  R1 = R2 = Me 1    67529 13  R1 = methyl, R2 = 4-methyl-3-heptenyl1    56000 14  R1 = H, R2 = t-butyl 1.5  47373 15  R1 = methyl, R2 =cyclopropyl 1    30118 16  R1 = methyl, R2 = phenyl 2    12118 17  R1 =H, R2 = phenyl 2    5647 18  R1 = methyl, R2 = 2-hydroxyethyl 5    117619  R1 = R2 = phenyl 5   less than 500 20  R1 = H, R2 = 2-pyrrolyl 5  less than 500 21 

2   less than 500 22 

2   less than 500 23* methylcyclopentadiene 2    1647 24*t-butylcyclopentadiene 2    1176 *comparative

Examples 25-44

In Examples 25-44 a series of ethylene/1-hexene copolymers were madeusing the slurry polymerization technique outlined above with catalystcompositions according to the invention made from a variety of zirconiumsalts, pentamethylenefulvene, and MMAO or methylaluminoxane (MAOcommercially available from Akzo Chemicals, Inc.) Catalyst compositionsolutions were prepared and tested under the same conditions as Examples1-24 with exceptions noted in Table 2, which gives the results.

As noted in Table 2, various aging times (i.e., contact times ofcatalyst composition ingredients) were used to form the catalystcompositions. In addition, some of the catalyst compositions were formedin the presence of 1-hexene as an olefin adjuvant. “%-Hexene adjuvant”is the volume percent 1-hexene in the final solution of activatedcatalyst composition.

TABLE 2 aging vol % time 1-hexene g PE/mmol Example Zr salt (hrs)adjuvant μmol cat Zr/100 psi/hr 25 Zr(NEt2)4 0.5 0 0.5 189647  26Zr(NEt2)4 0.5 0 0.5 238118  27 Zr(NEt2)4 (1) 0.5 0 0.3 289412  28Zr(NEt2)4 5 0 0.5 68706 29 Zr(NEt2)4 0.5 18 0.5 46588 30 Zr(NEt2)4 5 180.5 70588 31 Zr(acac)4 0.5 0 5  9647 32 Zr(acac)4 5 0 5  6965 33Zr(acac)4 0.5 37 5 18024 34 Zr(acac)4 5 37 5 19059 35 ZrBr4 0.5 0 519341 36 ZrBr4 5 0 5  8612 37 ZrBr4 0.5 40 3 15373 38 ZrBr4 5 40 3 3615739 Zr(acac-F6)4 0.5 0 1  6118 40 Zr(acac-F6)4 5 0 1.5 12549 41Zr(acac-F6)4 0.5 38 5 14635 42 Zr(acac-F6)4 5 38 3 22353 43 Zr(TMHD)40.5 0 0.5 less than 500 44 Zr(TMHD)4 5 0 1.5 17412 Zr(acac-F6)4 =zirconium (IV) 1,1,1,5,5,5-hexafluoro-2,4-pentandionate Zr(TMHD)4 =zirconium (IV) tetrakis(2,2,6,6-tetramethyl-3,5-heptandionate). (1) UsedMAO instead of MMAO.

Examples 45-63

In Examples 45-63 a series of ethylene/1-hexene copolymers (except forExample 47, an ethylene homopolymer) were made using the slurrypolymerization technique outlined above with catalyst compositionsaccording to the invention made from a variety of zirconium salts,6,6-dimethylfulvene, and MMAO or MAO. Catalyst solutions were preparedand tested under the same conditions as Examples 1-24 with exceptionsnoted in Table 3, which gives the results.

Various aging times (i.e., contact times of catalyst compositioningredients) were used to form the catalyst compositions.

TABLE 3 aging g PE/ time fulvene/ μmol mmol Zr/ Example Zr salt (hrs) ZrZr 100 psi/hr 45 Zr(NEt2)4 0.5 1 2 39412 46 Zr(NEt2)4 5 1 2 41412 47Zr(NEt2)4 (2) 0.5 1 2 24118 48 Zr(NEt2)4 0.5 2 1 67529 49 Zr(NEt2)4 (1)0.5 1 1 41882 50 Zr(NEt2)4 (1) 0.5 2 0.5 149647  51 ZrC14 (1) 0.5 2 5 4094 52 ZrC14 (1) 5 2 5  9788 53 ZrC14 (1) 0.5 4 5  1788 54 ZrC14 (1) 54 5  5976 55 Zr(O2CCMe3)4 0.5 1 2  8824 56 Zr(O2CCMe3)4 0.5 2 2 19176 57Zr(O2CCMe3)4 5 2 2 20706 58 Zr(O2CNiPr2)4 0.5 1 2 10824 59 Zr(O2CNIPr2)45 1 2  8706 60 Zr(acac-F6)4 0.5 1 5 18635 61 Zr(acac-F6)4 5 1 5 17600 62Zr(acac-F6)4 0.5 2 5 24141 63 Zr(acac-F6)4 5 2 5 22965 Zr(acac-F6)4Zirconium (IV) 1,1,1,5,5,5-hexafluoro-2,4-pentandionate (1) Used MAOinstead of MMAO. (2) No 1-hexene co-monomer in reactor.

Examples 64-78

In Examples 64-78 a series of ethylene/1-hexene copolymers were madeusing the slurry polymerization technique outlined above with catalystcompositions according to the invention made using a variety offulvene/Zr ratios. Catalyst solutions were prepared and tested under thesame conditions as Examples 1-24 with exceptions noted in Table 4, whichgives the results.

TABLE 4 Ex- ful- am- vene/ μmol g PE/mmol ple fulvene Zr salt Zr ZrZr/100 psi/hr 64 dimethylfulvene Zr(acac-F6)4 1 5 18635 65dimethylfulvene Zr(acac-F6)4 2 5 24141 66 dimethylfulvene Zr(NEt2)4 1 239412 67 dimethylfulvene Zr(NEt2)4 1.5 1.5 73569 68 dimethylfulveneZr(NEt2)4 2 1 67529 69 dimethylfulvene Zr(NEt2)4 4 1 96235 70dimethylfulvene ZrC14 (1) 2 5  4094 71 dimethylfulvene ZrC14 (1) 4 5 1788 72 dimethylfulvene Zr(O2CCMe3)4 1 2  8824 73 dimethylfulveneZr(O2CCMe3)4 2 2 19176 74 pentamethylene- Zr(NEt2)4 1 1 51765 fulvene 75pentamethylene- Zr(NEt2)4 2 0.5 212706 fulvene 76 pentamethylene-Zr(NEt2)4 3 0.4 154706 fulvene 77 pentamethylene- ZrBr4 1 6  1333fulvene 78 pentamethylene ZrBr4 2 5 19341 fulvene Zr(acac-F6)4 =Zirconium (IV) 1,1,1,5,5,5-hexafluoropentandionate (1) Used MAO insteadof MMAO

Examples 79-82

In Examples 79-82, a series of ethylene/1-hexene copolymers were madeusing the slurry polymerization technique outlined above with catalystcompositions according to the invention made by contacting mixtures ofpentamethylenefulvene (A) and 6-methyl-6-phenylfulvene (B) withZr(NEt₂)₄ and MMAO (2 moles fulvenes A+B/1 mole Zr).

Catalyst solutions were prepared and tested under the same conditions asExamples 1-24 with exceptions noted in Table 5, which gives the results.

TABLE 5 g PE/mmol Zr/100 Example ratio A/B μmol Zr psi/hr 79 1/8 6  352980 1/4 3  9569 81 1/2 1.5 27922 82 1/1 1.5 64314

Examples 83-100

In Examples 83-100, a series of ethylene/l-hexene copolymers were madeusing the slurry polymerization technique outlined above with catalystcompositions according to the invention made using 1) varios contacttimes between the fulvene/zirconium compound mixture and cocatalyst, 2)various zirconium concentrations, and 3) varios amounts of olefinadjuvant. Pentamethylenefulvene was used as the fulvene, with a 2/1 moleratio of fulvene to Zr. MMAO or MAO was used as the cocatalyst. Catalystcomposition solutions were prepared and under the same conditions asExamples 1-24 with exceptions noted in Table 6.

TABLE 6 contact % 1- Ex- time [Zr] hexene μmol g PE/mmol ample Zr salt(hrs) (mM) adjuvant cat Zr/100 psi/hr 83 Zr(NEt2)4 0.17 3.5 0 0.5172706  84 Zr(NEt2)4 0.5 3.5 0 0.5 238118  85 Zr(NEt2)4 1 3.5 0 0.5141647  86 Zr(NEt2)4 0.5 1 0 0.5 214588  87 Zr(NEt2)4 5 1 0 0.5 68706 88Zr(NEt2)4 0.5 3.5 20 0.5 46588 89 Zr(NEt2)4 5 3.5 20 0.5 70588 90Zr(acac-F6)4 0.5 1 0 1  6118 91 Zr(acac-F6)4 5 1 0 1.5 12549 92Zr(acac-F6)4 0.5 1 37 5 14635 93 Zr(acac-F6)4 5 1 37 3 22353 94Zr(acac)4 0.5 1 0 5  9647 95 Zr(acac)4 0.5 1 37 5 18024 96 Zr(acac)4 5 137 5 19059 97 ZrBr4 0.5 1 0 5 19341 98 ZrBr4 5 1 0 5  8612 99 ZrBr4 0.51 37 3 15373 100  ZrBr4 5 1 37 3 36157 Zr(acac-F6)4 = Zirconium (IV)1,1,1,5,5,5-hexafluoro-2,4-pentandionate (1) Used MAO instead of MMAO

Example 101

A 2/1 pentamethylenefulvene/Zr(NEt₂)₄ solution, 0.05M Zr in hexanesolvent, was mixed in-line with MMAO and was used as the catalystcomposition to produce an ethylene/1-hexene copolymer (density 0.917,1.0 melt index) in a pilot-scale, fluidized bed, gas phase reactor. Thereactor was nominally 14 inches in diameter and was operated with a bedheight of 6 feet and a superficial gas velocity of approximately 2ft/sec. Total reactor pressure was 350 psig.

First, a seed bed was charged to the reactor and it was dried to lessthan 10 ppm water. The reactor was pressurized to 150 psig of nitrogenand then 200 cc/hr of 5% teal in isopentane were fed to the reactor overone hour and allowed to circulate for one hour. The 1-hexene/ethylenemole ratio in the reactor was established at 0.025 and the temperaturewas 75° C.

The catalyst composition was made by mixing a 2/1pentamethylenefulvene/Zr(NEt₂)₄ solution, 0.05M Zr in hexane solvent,with MMAO (type 3A, 3.4 wt % Al, commercially available from AkzoChemicals, Inc.). Additional dilution of the catalyst composition wasperformed by adding hexane to the mixture. The catalyst composition inliquid form was sprayed into the reactor through a catalyst injectiontube with the aid of an atomizing nitrogen flow and a cycle gas purgeflow diverted from the rest of the cycle gas.

The reactor was started up as described above and then operated at thefollowing conditions:

Temperature: 75° C. Pressure: 350 psig Ethylene Partial Pressure: 220psi Bed Weight: 100 lbs 1-hexene to ethylene molar ratio: 0.022 Hydrogenconcentration: 200-300 ppm

The activity of the catalyst composition was dependent on the contacttime between MMAO and the pentamethylenefulvene/Zr(Et₂)₄ mixture. Table7 summarizes nthe changes inn activity with changing contact time.

TABLE 7 Less than 5 30 to 40 Contact Time minutes minutes Zr ppmw 7.72  3 gPE/mmole Zr/hr/100 C2 psi 1534 3000

I claim:
 1. A process for the polymerization of olefins, which comprisescontacting under polymerization conditions one or more olefins with acatalyst composition comprising the reaction product of: a) a fulvene ofthe formula:

including oligomers thereof, wherein each R₁, R₂, R₃, R₄, R₅, and R₆ isindependently hydrogen, hydrocarbyl, or a heteroatom-containing group;and any two or more R₁₋₆ groups may be joined to form a ring; b) acomplex of the formula [L_(m)MX_(n)]_(r) wherein each L is a neutralligand selected from the group consisting of diethylether,tetrahydrofuran, triethylamine and pyridine, M is a metal selected fromGroups 3 to 6 and the Lanthanides, each X is an anionic group selectedfrom the group consisting of alkoxide, amide, acetylacetonate,carbamate, amidate and aluminate groups, m is an integer of 0 orgreater, n is an integer of 0 or greater selected to provide chargeneutrality in the complex, and r is an integer of 1 or greater; and c)an activating cocatalyst.
 2. The process of claim 1, wherein the fulveneis a 6,6-dialkylfulvene.
 3. The process of claim 1, wherein the fulveneis selected from the group consisting of 6,6-dimethylfulvene,6-t-butylfulvene, 6-methyl-6-phenylfulvene, 6,6-tetramethylenefulvene,and 6,6-pentamethylenefulvene.
 4. The process of claim 1, wherein M froma Group 4 metal.
 5. The process of claim 1, wherein the fulvene is6,6-pentamethylenefulvene, the complex is a zirconium (IV)acetylacetonate- or zirconium (IV) diethylamide-complex, and theactivating cocatalyst is modified methylaluminoxane.
 6. The process ofclaim 1, wherein the catalyst composition is in liquid form.
 7. Theprocess of claim 1, wherein the catalyst composition further comprisesan olefin adjuvant.
 8. The process of claim 7, wherein the olefinadjuvant is ethylene, propylene, 1-butene, 2-butene, 1-hexene,isobutylene, diisobutylene or a diene.
 9. The process of claim 8,wherein the olefin adjuvant is 1-butene or 1-hexene.
 10. The process ofclaim 1 conducted in the gas phase.
 11. A process for the polymerizationof olefins, which comprises contacting under polymerization conditionsone or more olefins with a catalyst composition comprising the reactionproduct of: a) a fulvene of the formula:

including oligomers thereof, wherein each R₁, R₂, R₃, R₄, R₅, and R₆ isindependently hydrogen, hydrocarbyl, or a heteroatom-containing group;and any two or more R₁₋₆ groups may be joined to form a ring; b) acomplex of the formula [L_(m)MX_(n)]_(r) wherein each L is a neutralligand, M is a metal selected from Groups 3 to 6 and the Lanthanides,each X is an anionic group, m is an integer of 0 or greater, n is aninteger of 0 or greater selected to provide charge neutrality in thecomplex, and r is an integer of 1 or greater; c) an olefin adjuvant; andd) an activating cocatalyst with the proviso that the olefin adjuvant iscontacted with a) and b) prior to contact with d).
 12. The process ofclaim 11, wherein the fulvene is a 6,6-dialkylfulvene.
 13. The processof claim 11, wherein the fulvene is selected from the group consistingof 6,6-dimethylfulvene, 6-t-butylfulvene, 6-methyl-6-phenylfulvene,6,6-tetramethylenefulvene, and 6,6-pentamethylenefulvene.
 14. Theprocess of claim 11, wherein M is a Group 4 metal.
 15. The process ofclaim 11, wherein the fulvene is 6,6-pentamethylenefulvene, the complexis a zirconium (IV) acetylacetonate- or zirconium (IV)diethylamide-complex, and the activating cocatalyst is modifiedmethylaluminoxane.
 16. The process of claim 11, wherein the catalystcomposition is in liquid form.
 17. The process of claim 11, wherein theolefin adjuvant is ethylene, propylene, 1-butene, 2-butene, 1-hexene,isobutylene, diisobutylene or a diene.
 18. The process of claim 11,wherein the olefin adjuvant is 1-butene or 1-hexene.
 19. The process ofclaim 11, wherein ethylene and optionally a higher alpha-olefin selectedfrom the group consisting of propylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1 -octene, and 3,5,5-trimethyl-1-hexene ispolymerized.
 20. The process of claim 11 conducted in the gas phase.